Mixtures of Reactive Dyes and Their Use

ABSTRACT

Provided are processes for dyeing or printing fibre materials using reactive dye mixtures. The reactive dyes mixtures have been found to be suitable for dyeing or printing hydroxyl-group containing fibre materials or nitrogen-containing fibre materials. The dyeings or prints obtained according to such processes exhibit good all around fastness properties.

This application is a divisional application of U.S. patent applicationSer. No. 13/747,575, currently pending, which was a divisionalapplication of U.S. patent application Ser. No. 12/711,774, abandoned,which was a continuation of U.S. patent application Ser. No. 10/592,888,abandoned, which was the National Phase of International ApplicationPCT/EP2005/051037 filed Mar. 9, 2005 which designated the U.S. and whichclaims priority to European Pat. App. No. 04101142.0 filed Mar. 19,2004. The noted applications are incorporated herein by reference.

FIELD OF INVENTION

The present invention relates to mixtures of reactive dyes, whichmixtures are suitable for dyeing or printing nitrogen-containing orhydroxy-group-containing fibre materials and yield dyeings or printshaving good all-round fastness properties.

BACKGROUND OF THE INVENTION

The practice of dyeing has recently led to higher demands being made onthe quality of the dyeings and the economic efficiency of the dyeingprocess. As a result, there continues to be a need for novel, readilyobtainable dyeing compositions having good properties, especially inrespect of their application.

Dyeing today requires reactive dyes that, for example, have sufficientsubstantivity and at the same time exhibit good ease of washing-off ofunfixed dye. In addition, they should exhibit a good colour yield and ahigh reactivity, the objective being especially to obtain dyeings havinghigh degrees of fixing. In many cases the build-up behaviour of reactivedyes is not sufficient to meet the demands made, especially when dyeingin very deep shades.

The problem underlying the present invention is therefore to providenovel mixtures of reactive dyes, which mixtures are especially suitablefor dyeing and printing fibre materials and possess the above-describedqualities to a high degree. They should also yield dyeings having goodall-round fastness properties, for example fastness to light and towetting.

SUMMARY OF THE INVENTION

The present invention accordingly relates to dye mixtures comprising atleast one dye, for example one, two or three dyes, preferably one dye,of formula

and at least one dye, for example one, two or three dyes, from the groupof formulae

wherein(R₁)_(b) denotes b identical or different substituents from the groupC₁-C₄ alkyl, C₁-C₄ alkoxy, sulfo and halogen,R₂, R₃, R₄ and R₅ are each independently of the others hydrogen, C₁-C₄alkyl, C₁-C₄ alkoxy, sulfo or halogen,G is a phenylene radical that is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy or by sulfo, or is a cyclohexylene,phenylenemethylene or C₂-C₆alkylene radical,one of the radicals Q₁ and Q₂ is amino and the other of the radicals Q₄and Q₂ is hydroxy,X₁ is halogen,Y₁, Y₂ and Y₃ are each independently of the others a fibre-reactiveradical of formula

—SO₂—Z  (5a),

—NH—CO—(CH₂)_(m)—SO₂—Z  (5b),

—CONH—(CH₂)_(n)—SO₂—Z  (5c),

—NH—CO—CH(Hal)-CH₂-Hal  (5d),

—NH—CO—C(Hal)=CH₂  (5e) or

whereinX₂ is halogen,T₂ independently has the definition of X₂, is a non-fibre-reactivesubstituent or is a fibre-reactive radical of formula

—NH—(CH₂)₂₋₃—SO₂—Z  (6a),

—NH—(CH₂)₂₋₃—O—(CH₂)₂₋₃-SO₂—Z  (6b),

(R₆)₀₋₂ denotes from 0 to 2 identical or different substituents from thegroup halogen, C₁-C₄ alkyl, C₁-C₄alkoxy and sulfa,Z is vinyl or a —CH₂—CH₂—U radical and U is a group that is removableunder alkaline conditions,Q is a —CH(Hal)-CH₂-Hal or —C(Hal)=CH₂ group,m and n are each independently of the other the number 2, 3 or 4, andHal is halogen,T₁ is a fibre-reactive radical of the above-mentioned formula (6b),(6c), (6d) or (6e), andb and k are each independently of the other the number 0, 1 or 2.

DETAILED DESCRIPTION OF THE INVENTION

A suitable combination of at least one, two or three dyes from the groupof formulae (2), (3) and (4) is, for example, one or two dyes of formula(2); one or two dyes of formula (3); or one or two dyes of formula (4);one dye of formula (2) and one dye of formula (3); one dye of formula(2) and one dye of formula (4); or one dye of formula (3) and one dye offormula (4); or one dye of formula (2), one dye of formula (3) and onedye of formula (4); preferably one dye of formula (2), one dye offormula (3), or one dye of formula (4).

As C₁-C₄ alkyl there come into consideration for R₁, R₂, R₃, R₄, R₅, R₆and the corresponding radicals in the bridging member G, eachindependently of the others, for example, methyl, ethyl, propyl,isopropyl, butyl, sec-butyl, tert-butyl and isobutyl, preferably methyland ethyl and especially methyl.

As C₁-C₄ alkoxy there come into consideration for R₁, R₂, R₃, R₄, R₅, R₆and the corresponding radicals in the bridging member G, eachindependently of the others, for example, methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy and isobutoxy, preferably methoxy and ethoxy andespecially methoxy.

As halogen there come into consideration for R₁, R₂, R₃, R₄, R₅, R₆ andthe corresponding radicals in the bridging member G, each independentlyof the others, for example, fluorine, chlorine and bromine, preferablychlorine and bromine and especially chlorine.

As a C₂-C₆ alkylene radical for the bridging member G there come intoconsideration a branched or unbranched radical, such as, for example,1,2-ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1,3-butylene,1,5-pentylene, 3,5-pentylene, 1,6-hexylene, 2,5-hexylene, 4,6-hexyleneand the radicals of formulae

For X₁ and X₂, each independently of the other, there come intoconsideration, for example, fluorine, chlorine and bromine, preferablyfluorine and chlorine. X₁ is especially chlorine.

As the leaving group U there come into consideration, for example, —Cl,—Br, —F, —OSO₃H, —SSO₃H, —OCO—CH₃, —OPO₃H₂, —OCO—C₆H₅, —OSO₂—C₁-C₄ alkyland —OSO₂—N(C₁-C₄ alkyl)₂. Preferably, U is a group of formula —Cl,—OSO₃H, —SSO₃H, —OCO—CH₃, —OCO—C₆H₆ or —OPO₃H₂, especially —Cl or —OSO₃Hand more especially —OSO₃H.

Examples of suitable radicals Z are accordingly vinyl, β-bromo- orβ-chloroethyl, β-acetoxyethyl, β-benzoyloxyethyl, β-phosphatoethyl,β-sulfatoethyl and β-thiosulfatoethyl.

Preferably, Z is independently vinyl, β-chloroethyl or β-sulfatoethyl,especially vinyl or β-sulfatoethyl.

Preferably, (R₁)_(b), denotes b identical or different substituents fromthe group C₁-C₄ alkyl, C₁-C₄ alkoxy and sulfo, especially b sulfosubstituents.

Preferably, R₂, R₃, R₄ and R₅ are each independently of the othershydrogen, C₁-C₄ alkyl, C₁-C₄ alkoxy or sulfo, especially hydrogen,methyl, methoxy or sulfo.

R₄ and R₅ are especially preferably hydrogen.

(R₆)₀₋₂ denotes preferably from 0 to 2 identical or differentsubstituents from the group C₁-C₄ alkyl, C₁-C₄alkoxy and set),especially methyl, methoxy and sulfo.

R₆ is especially preferably hydrogen.G is preferably an unsubstituted phenylene radical or a phenyleneradical substituted by C₁-C₄ alkyl, C₁-C₄alkoxy, halogen, carboxy or bysulfo.

Preferably, T₁ is a radical of formula (6b), (6c) or (6d), especially offormula (6c), the definitions and preferred meanings given hereinbeforeapplying to the variables.

In an embodiment of interest, T₁ is a radical of formula

wherein(R₆)₀₋₂ and Z each have the definitions and preferred meanings givenhereinbefore.

T₂ is preferably a non-fibre-reactive substituent or a fibre-reactiveradical of formula (6a), (6b), (6c), (6d) or (6e).

As a fibre-reactive radical, T₂ is preferably a radical of formula (6b),(6c), (6d) or (6e), especially of formula (6b), (6c) or (6d), and moreespecially of formula (6c), the definitions and preferred meanings givenhereinbefore applying to the variables.

When T₂ is a non-fibre-reactive substituent it may be, for example,hydroxy; C₁-C₄alkoxy; C₁-C₄alkylthio unsubstituted or substituted, forexample, by hydroxy, carboxy or by sulfa; amino; amino mono- ordi-substituted by C₁-C₈alkyl, wherein the alkyl is unsubstituted or isfurther substituted, for example, by sulfo, sulfato, hydroxy, carboxy orby phenyl, especially by sulfo or by hydroxy, and may be interrupted oneor more times by the radical —O—; cyclohexylamino; morpholino; N—C₁-C₄alkyl-N-phenylamino or phenylamino or naphthylamino, wherein the phenylor naphthyl is unsubstituted or substituted, for example, by C₁-C₄alkyl,C₁-C₄alkoxy, C₂-C₄ alkanoylamino, carboxy, sulfo or by halogen and thealkyl is unsubstituted or substituted, for example, by hydroxy, sulfo orby sulfato.

Examples of suitable non-fibre-reactive substituents T₂ are amino,methylamino, ethylamino, β-hydroxyethylamino,N-methyl-N-β-hydroxyethylamino, N-ethyl-N-β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, β-sulfoethylamino, cyclohexylamino,morpholino, 2-, 3- or 4-chlorophenylamino, 2-, 3- or4-methylphenylamino, 2-, 3- or 4-methoxyphenylamino, 2-, 3- or4-sulfophenylamino, 2,5-disulfophenylamino, 2-, 3- or4-carboxyphenylamino, 1- or 2-naphthylamino, 1-sulfo-2-naphthylamino,4,8-disulfo-2-naphthylamino, N-ethyl-N-phenylamino,N-methyl-N-phenylamino, methoxy, ethoxy, n- or iso-propoxy and hydroxy.

As a non-fibre-reactive substituent, T₂ preferably has the definitionC₁-C₄ alkoxy; C₁-C₄ alkylthio that is unsubstituted or substituted byhydroxy, carboxy or by sulfo; hydroxy; amino; N-mono- orN,N-di-C₁-C₄alkylamino that is unsubstituted or substituted in the alkylmoiety/moieties by hydroxy, sulfato or by sulfo; morpholino; phenylaminothat is unsubstituted or substituted in the phenyl ring by sulfo,carboxy, acetylamino, chlorine, methyl or by methoxy; orN—C₁-C₄alkyl-N-phenylamino that is unsubstituted or substituted in thesame way on the phenyl ring, wherein the alkyl is unsubstituted orsubstituted by hydroxy, sulfa or by sulfato; or naphthylamino that isunsubstituted or substituted by from 1 to 3 sulfo groups.

Non-fibre-reactive substituents T₂ to which special preference is givenare amino, N-methylamino, N-ethylamino, N-β-hydroxyethylamino,N-methyl-N-β-hydroxyethylamino, N-ethyl-N-β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, 3-sulfoethylamino, morpholino, 2-, 3- or4-carboxyphenylamino, 2-, 3- or 4-sulfophenylamino,2,5-disulfophenylamino and N—C₁-C₄alkyl-N-phenylamino.

In the case of the fibre-reactive radicals T₂ of formulae (6a) and (6b),Z is preferably vinyl or β-chloroethyl. In the case of thefibre-reactive radicals T₂ of formulae (6c) and (6d), Z is preferablyvinyl or β-sulfatoethyl.

In an embodiment of interest, T₂ is one of the above-mentionedfibre-reactive radicals.

Hal in the fibre-reactive radicals of formulae (5d), (5e) and (6e) ispreferably chlorine or bromine, especially bromine.

Preferably, Y₁ is a radical of formula (5a), (5b), (5c), (5d) or (5e),especially of formula (5a), (5b) or (5c) and more especially of formula(5a), the definitions and preferred meanings given above applying to thevariables.

Preferably, Y₂ is a radical of formula (5a) or (50, especially offormula (5a), the definitions and preferred meanings given aboveapplying to the variables,

Preferably, Y₃ is a radical of formula (5a) or (5f), especially offormula (5a), the definitions and preferred meanings given aboveapplying to the variables. When Y₃ is a radical of formula (5f), T₂denoting a radical of formula (6b) or (6c), especially (6b), is ofinterest.

b is preferably the number 1 or 2 and especially the number 1.

k is preferably the number 1 or 2 and especially the number 1.

m and n are preferably each independently of the other the number 2 or3.

m is especially preferably the number 3.

n is especially preferably the number 2.

The dye of formula (1) is preferably a dye of formula

whereinT₁, X₁, Y₁ and k each have the definitions and preferred meanings givenabove.

The dye of formula (2) is preferably a dye of formula

whereinR₂ is hydrogen or C₁-C₄ alkoxy, preferably C₁-C₄ alkoxy,R₃ is hydrogen, C₁-C₄ alkyl or C₁-C₄ alkoxy, andeach Z, independently, has the definition and preferred meanings givenabove.R₂ is especially preferably methoxy.R₃ is especially preferably hydrogen, methyl or methoxy, especiallyhydrogen.

The dye of formula (3) is preferably a dye of formula

wherein(R₇)₀₋₄ denotes from 0 to 4 identical or different substituents from thegroup C₁-C₄ alkyl, alkoxy, halogen, carboxy and sulfo, preferably fromthe group C₁-C₄alkyl, C₁-C₄ alkoxy and sulfo andY₂ has the definition and preferred meanings given above.

The dye of formula (4) is preferably a dye of formula

whereinY₃ has the definition and preferred meanings given above.

A dye of formula (1) to which special preference is given is a dye offormula

whereinX₁ is halogen, especially chlorine, andeach Z independently has the definition and preferred meanings givenabove and is preferably vinyl or β-sulfatoethyl.

The dye of formula (1) is, for example, a dye of formula

preferably of formula (1.1).

The dye of formula (2) is, for example, a dye of formula

preferably of formula (2.1).

The dye of formula (3) is, for example, a dye of formula

preferably of formula (3.1).

The dye of formula (4) is, for example, a dye of formula

preferably of formula (4.1) or (4.2), especially of formula (4.1).

The reactive dyes of formulae (1) to (4) in the dye mixtures accordingto the invention contain sulfo groups, each of which is either in theform of the free sulfonic acid or, preferably, in the form of a saltthereof, for example in the form of the sodium, lithium, potassium orammonium salt, or in the form of a salt of an organic amine, for examplein the form of the triethanol-ammonium salt.

The reactive dyes of formulae (1) to (4), and therefore also the dyemixtures, may comprise further additives, for example sodium chloride ordextrin.

The dyes of formula (1) and the total amount of the dyes of formulae(2), (3) and (4) are present in the dye mixture according to theinvention in a weight ratio of, for example, from 1:99 to 99:1,preferably from 5:95 to 95:5 and especially from 10:90 to 90:10.

The dyes of formulae (1), (2), (3) and (4) are known or can be preparedaccording to methods known per se. Dyes of formula (1) are described,for example, in U.S. Pat. No. 4,622,390.

Dyes of formula (2) are disclosed, for example, in DE 960 534, DE 31 13989 A1, EP 0 063 276 A2 and EP 0 122 600 A1. Dyes of formula (3) areknown, for example, from U.S. Pat. No. 3,558,621, U.S. Pat. No.4,631,341, U.S. Pat. No. 4,754,023, GB 2 034 731 A and EP 0 064 250 A1.Dyes of formula (4) are described, for example, in U.S. Pat. No.4,336,190 and U.S. Pat. No. 4,754,023.

The dye mixtures according to the invention can be prepared, forexample, by mixing the individual dyes. Such a mixing process is carriedout, for example, in suitable mills, for example ball mills or pinmills, and also in kneaders or mixers.

The dye mixtures according to the invention may, where appropriate,comprise further auxiliaries that, for example, improve handling orincrease storage stability, such as, for example, buffers, dispersantsor anti-dusts. Such auxiliaries are known to the person skilled in theart.

The dye mixtures according to the invention are suitable for dyeing andprinting an extremely wide variety of materials, especiallyhydroxyl-group-containing or nitrogen-containing fibre materials.Examples are paper, silk, leather, wool, polyimide fibres andpolyurethanes and also especially cellulosic fibre materials of allkinds. Such fibre materials are, for example, the natural cellulosicfibres, such as cotton, linen and hemp, and also cellulose andregener-ated cellulose. The dye mixtures according to the invention arealso suitable for dyeing or printing hydroxyl-group-containing fibrespresent in blend fabrics, e.g. mixtures of cotton with polyester fibresor polyamide fibres.

The present invention accordingly relates also to the use of the dyemixtures according to the invention in the dyeing or printing ofhydroxyl-group-containing or nitrogen-containing, especiallycellulose-containing, fibre materials.

The dye mixtures according to the invention can be applied to the fibrematerial and fixed to the fibre in a variety of ways, especially in theform of aqueous dye solutions and dye print pastes. They are suitableboth for the exhaust method and for dyeing in accordance with thepad-dyeing method; they can be used at low dyeing temperatures andrequire only short steaming times in the pad-steam process. The build-upbehaviour is very good, the degrees of fixing are high and unfixed dyecan be washed off easily, the difference between the degree of exhaustand the degree of fixing being remarkably small, that is to say thesoaping loss is very low. The dye mixtures according to the inventionare also suitable for printing, especially on cotton, but are equallysuitable also for printing nitrogen-containing fibres, for example woolor silk or blend fabrics that contain wool.

The dyeings and prints produced using the dye mixtures according to theinvention can be reproduced very well, have a high tinctorial strengthand a high fibre-to-dye binding stability in both the acidic and thealkaline range, and furthermore have good fastness to light and verygood wet-fastness properties, such as fastness to washing, to water, tosea water, to cross-dyeing and to perspiration. The dyeings obtainedexhibit fibre levelness and surface levelness.

The dye mixtures according to the invention are also suitable ascolorants for use in recording systems. Such recording systems are, forexample, commercially available inkjet printers for paper or textileprinting, or writing instruments, such as fountain pens or ballpointpens and especially inkjet printers. For that purpose the dye mixtureaccording to the invention is first brought into a form suitable for usein recording systems. A suitable form is, for example, an aqueous inkthat comprises the dye mixture according to the invention as colorant.The inks can be prepared in customary manner by mixing together theindividual constituents in the desired amount of water.

Substrates that come into consideration include the above-mentionedhydroxyl-group-containing or nitrogen-containing fibre materials,especially cellulose-containing fibre materials.

The dyes used in the aqueous inks should preferably have a low saltcontent, that is to say they should have a total content of salts ofless than 0.5% by weight, based on the weight of the dyes. Dyes thathave relatively high salt contents as a result of their preparationand/or as a result of the subsequent addition of diluents can be saltedout, for example, by membrane separation procedures, such asultrafiltration, reverse osmosis or dialysis.

The inks preferably have a total content of dyes of from 1 to 35% byweight, especially from 1 to 30% by weight and preferably from 1 to 20%by weight, based on the total weight of the ink. The preferred lowerlimit in this case is a limit of 1.5% by weight, preferably 2% by weightand especially 3% by weight.

The inks may comprise water-miscible organic solvents, for example C₁-C₄alcohols, e.g. methanol, ethanol, n-propanol, isopropanol, n-butanol,sec-butanol, tert-butanol or iso-butanol; amides, e.g. dimethylformamideor dimethylacetamide; ketones or ketone alcohols, e.g. acetone,diacetone alcohol; ethers, e.g. tetrahydrofuran or dioxane;nitrogen-containing heterocyclic compounds, e.g. N-methyl-2-pyrrolidoneor 1,3-dimethyl-2-imidazolidone, polyalkylene glycols, e.g. polyethyleneglycol or polypropylene glycol; C₂-C₆ alkylene glycols and thioglycols,e.g. ethylene glycol, propylene glycol, butylene glycol, triethyleneglycol, thio-diglycol, hexylene glycol and diethylene glycol; otherpolyols, e.g. glycerol or 1,2,6-hexane-triol; and C₁-C₄ alkyl ethers ofpolyhydric alcohols, e.g. 2-methoxyethanol, 2-(2-methoxy-ethoxy)ethanol,2-(2-ethoxyethoxy)ethanol, 2-[2-(2-methoxyethoxy)ethoxy]ethanol or2-[2-(2-ethoxyethoxy)ethoxy]ethanol; preferably N-methyl-2-pyrrolidone,diethylene glycol, glycerol or especially 1,2-propylene glycol, usuallyin an amount of from 2 to 30% by weight, especially from 5 to 30% byweight and preferably from 10 to 25% by weight, based on the totalweight of the ink.

In addition, the inks may also comprise solubilisers, e.g.s-caprolactam.

The inks may comprise thickeners of natural or synthetic origin interalia for the purpose of adjusting the viscosity.

Examples of thickeners that may be mentioned include commerciallyavailable alginate thickeners, starch ethers or locust bean flourethers, especially sodium alginate on its own or in admixture withmodified cellulose, e.g. methyl cellulose, ethyl cellulose,carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethylcellulose, hydroxypropyl cellulose or hydroxypropyl methyl cellulose,especially with preferably from 20 to 25% by weight carboxymethylcellulose. Synthetic thickeners that may be mentioned are, for example,those based on poly(meth)acrylic acids or poly(meth)acrylamides and alsopolyalkylene glycols having a molecular weight of e.g. from 2000 to 20000, for example polyethylene glycol or polypropylene glycol or themixed polyalkylene glycols of ethylene oxide and propylene oxide.

The inks comprise such thickeners, for example, in an amount of from0.01 to 2% by weight, especially from 0.01 to 1% by weight andpreferably from 0.01 to 0.5% by weight, based on the total weight of theink.

The inks may also comprise buffer substances, e.g. borax, borates,phosphates, poly-phosphates or citrates. Examples that may be mentionedinclude borax, sodium borate, sodium tetraborate, sodium dihydrogenphosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodiumpentapolyphosphate and sodium citrate. They are used especially inamounts of from 0.1 to 3% by weight, preferably from 0.1 to 1% byweight, based on the total weight of the ink, in order to establish a pHvalue of, for example, from 4 to 9, especially from 5 to 8.5.

As further additives, the inks may comprise surfactants or humectants.

Suitable surfactants include commercially available anionic or non-ionicsurfactants. As humectants in the inks according to the invention therecome into consideration, for example, urea or a mixture of sodiumlactate (advantageously in the form of a 50% to 60% aqueous solution)and glycerol and/or propylene glycol in amounts of preferably from 0.1to 30% by weight, especially from 2 to 30% by weight.

Preference is given to inks having a viscosity of from 1 to 40 mPa·s,especially from 1 to 20 mPa·s and more especially from 1 to 10 mPa·s.

Furthermore, the inks may in addition comprise customary additives, e.g.anti-foams or especially preservatives that inhibit fungal and/orbacterial growth. Such additives are usually used in amounts of from0.01 to 1% by weight, based on the total weight of the ink.

Preservatives that come into consideration include formaldehyde-yieldingagents, e.g. paraformaldehyde and trioxane, especially aqueous,approximately 30 to 40% by weight formaldehyde solutions, imidazolecompounds, e.g. 2-(4-thiazolyl)benzimidazole, thiazole compounds, e.g.1,2-benzisothiazolin-3-one or 2-n-octyl-isothiazolin-3-one, iodinecompounds, nitrites, phenols, haloalkylthio compounds and pyridinederivatives, especially 1,2-benzisothiazolin-3-one or2-n-octyl-isothiazolin-3-one. A suitable preservative is e.g. a 20% byweight solution of 1,2-benzisothiazolin-3-one in dipropylene glycol(Proxel® GXL).

The inks may also comprise further additives, such as fluorinatedpolymers or telomers, e.g. polyethoxyperfluoroalcohols (Forafac® orZonyl® products) in an amount of e.g. from 0.01 to 1% by weight, basedon the total weight of the ink.

In inkjet printing, individual droplets of the ink are sprayed onto asubstrate in a controlled manner from a nozzle. For that purpose,predominantly the continuous inkjet method and the drop-on-demand methodare used. In the continuous inkjet method, the droplets are producedcontinuously and any droplets not required for the printing are conveyedto a collecting vessel and recycled, whereas in the drop-on-demandmethod droplets are produced and printed as required, that is to saydroplets are produced only when required for the printing. Theproduction of the droplets can be effected, for example, by means of apiezo-inkjet head or by means of thermal energy (bubble jet). Printingby means of a piezo-inkjet head and printing in accordance with thecontinuous inkjet method are preferred.

The present invention accordingly relates also to aqueous inkscomprising the dye mixtures according to the invention and to the use ofsuch inks in an inkjet printing method for the printing of varioussubstrates, especially textile fibre materials, the definitions andpreferred meanings given above applying to the dye mixtures, the inksand the substrates.

The following Examples serve to illustrate the invention. Unlessotherwise indicated, the temperatures are given in degrees Celsius,parts are parts by weight and percentages relate to % by weight. Partsby weight relate to parts by volume in a ratio of kilograms to litres.

Example 1

100 parts of a cotton fabric are introduced at a temperature of 60° C.into a dye bath containing 3.0 parts of the dye of formula (1.1), 3.0parts of the dye of formula (2.1) and 60 parts of sodium chloride in1000 parts of water. After 45 minutes at a temperature of 60° C., 20parts of calcined soda are added. The temperature of the dye bath ismaintained at 60° C. for a further 45 minutes. The dyed fabric is thenrinsed and dried in the usual manner. A navy-blue dyeing having goodfastness properties is obtained.

Examples 2 to 4

By proceeding as indicated in Example 1 but, instead of using 3.0 partsof the dye of formula (2.1), using 3.0 parts of the dye of formula(2.2), 3.0 parts of the dye of formula (2.3) or 3.0 parts of the dye offormula (2.4), there is likewise obtained a navy-blue dyeing having goodfastness properties.

In a manner analogous to that described in Example 1, instead of 3.0parts of the dye of formula (1.1), the same amount of one of the dyes offormulae (1.2), (1.3), (1.4), (1.5) and (1.6) may be used.

Example 5

100 parts of a cotton fabric are introduced at a temperature of 60° C.into a dye bath containing 3.0 parts of the dye of formula (1.1), 3.0parts of the dye of formula (3.1) and 60 parts of sodium chloride in1000 parts of water. After 45 minutes at a temperature of 60° C., 20parts of calcined soda are added. The temperature of the dye bath ismaintained at 60° C. for a further 45 minutes. The dyed fabric is thenrinsed and dried in the usual manner. A navy-blue dyeing having goodfastness properties is obtained.

Examples 6 to 11

By proceeding as indicated in Example 1 but, instead of using 3.0 partsof the dye of formula (3.1), using 3.0 parts of the dye of formula(3.2), 3.0 parts of the dye of formula (3.4), 3.0 parts of the dye offormula (3.5), 3.0 parts of the dye of formula (3.6), 3.0 parts of thedye of formula (3.7) or 3.0 parts of the dye of formula (3.8), there islikewise obtained a navy-blue dyeing having good fastness properties.

In a manner analogous to that described in Example 5, instead of 3.0parts of the dye of formula (1.1), the same amount of one of the dyes offormulae (1.2), (1.3), (1.4), (1.5) and (1.6) may be used.

Example 12

100 parts of a cotton fabric are introduced at a temperature of 60° C.into a dye bath containing 3.0 parts of the dye of formula (1.1), 3.0parts of the dye of formula (4.1) and 60 parts of sodium chloride in1000 parts of water. After 45 minutes at a temperature of 60° C., 20parts of calcined soda are added. The temperature of the dye bath ismaintained at 60° C. for a further 45 minutes. The dyed fabric is thenrinsed and dried in the usual manner. A navy-blue dyeing having goodfastness properties is obtained.

Examples 13 to 15

By proceeding as indicated in Example 12 but, instead of using 3.0 partsof the dye of formula (4.1), using 3.0 parts of the dye of formula(4.2), 3.0 parts of the dye of formula (4.3) or 3.0 parts of the dye offormula (4.4), there is likewise obtained a navy-blue dyeing having goodfastness properties.

In a manner analogous to that described in Example 12, instead of 3.0parts of the dye of formula (1.1), the same amount of one of the dyes offormulae (1.2), (1.3), (1.4), (1.5) and (1.6) may be used.

Example 16

10 parts of a woollen fabric are dyed in a laboratory dyeing apparatususing the following liquor:

0.2 part of sodium acetate,

-   0.5 part of 80% acetic acid,    0.2 part of a commercially available levelling agent (Albegal B®),    0.30 part of the dye of formula (1.3),    0.30 part of the dye of formula (3.3), and    200 parts of water.

The pH of the liquor is 4.5. The textile is treated in the dye liquorfor 5 min. at 40° C. and is then heated at a heating rate of 1°/min toboiling temperature (98° C.) and dyed at that temperature for 90minutes. After cooling the liquor to 80° C., a solution of 0.8 part ofsodium carbonate in 8 parts of water is added and the textile materialis treated for 20 min. at 80° C. and a pH of 8.5. The dyeing is thenrinsed and finished in the usual manner. A navy-blue dyeing exhibitingfibre levelness and surface levelness and having good fastnessproperties is obtained.

Example 17

By proceeding as indicated in Example 16 but, instead of using 0.30 partof the dye of formula (1.3), using 0.30 part of the dye of formula(1.4), there are likewise obtained navy-blue dyeings exhibiting fibrelevelness and surface levelness and having good fastness properties.

Example 18

Mercerised cotton satin is pad-dyed using a liquor containing 30 g/l ofsodium carbonate and 50 g/l of urea (70% liquor pick-up) and dried.

(b) Using a drop-on-demand inkjet head (bubble jet), the cotton satinpretreated according to step (a) is printed with an aqueous inkcontaining

-   -   10% by weight of a mixture of 3.0 parts of the reactive dye of        formula (1.1) and 3.0 parts of the reactive dye of formula        (2.1),    -   20% by weight of 1,2-propylene glycol and    -   70% by weight of water.

The print is fully dried and is fixed in saturated steam at 102° C. for8 minutes, cold-rinsed, washed-off at boiling temperature, rinsed againand dried.

A navy-blue print having good fastness properties is obtained.

What is claimed is:
 1. A process for printing of a substrate comprisingspraying individual droplets of an aqueous ink onto the substrate from anozzle in a controlled manner wherein the aqueous ink comprises a dyemixture consisting of at least one dye of formula

and at least one dye from the group of formulae

and optionally an additive selected from sodium chloride, dextrin, abuffer, a dispersant, an anti-dust, an organic solvent, a solubilizer, athickener, a surfactant, a humectant, an anti-foam, a preservative, afluorinated polymer, a telomer and a mixture thereof, wherein (R₁) issulfo, R₂ is C₁ alkoxy, R₃, R₄ and R₅ are each hydrogen, one of theradicals Q₁ and Q₂ is amino and the other of the radicals Q₁ and Q₂ ishydroxy, X₁ is chlorine, Y₁ and Y₃ are each a fibre-reactive radical offormula—SO₂—Z  (5a), T₁ is a fibre-reactive radical of formula

Z is a —CH₂—CH₂-U radical and U is a group that is removable underalkaline conditions, b is 1, and k is
 1. 2. The process of claim 1wherein the substrate is a textile fibre material.
 3. A method fordyeing fibre material which comprises: (i) applying a dye mixtureconsisting of at least one dye of formula

and at least one dye from the group of formulae

and optionally an additive selected from sodium chloride, dextrin, abuffer, a dispersant, an anti-dust, an organic solvent, a solubilizer, athickener, a surfactant, a humectant, an anti-foam, a preservative, afluorinated polymer, a telomer and a mixture thereof, wherein (R₁) issulfo, R₂ is C₁ alkoxy, R₃, R₄ and R₅ are each hydrogen, one of theradicals Q₁ and Q₂ is amino and the other of the radicals Q₁ and Q₂ ishydroxy, X₁ is chlorine, Y₁ and Y₃ are each a fibre-reactive radical offormula—SO₂—Z  (5a), T₁ is a fibre-reactive radical of formula

Z is a —CH₂—CH₂-U radical and U is a group that is removable underalkaline conditions, b is 1, and k is 1 to the fibre material; and (ii)fixing the dye mixture to the fibre material.
 4. The method according toclaim 3 wherein the fibre material is a hydroxyl-group-containing fibrematerial or a nitrogen-group-containing fibre material.
 5. The method ofclaim 3 wherein the fibre material is a cellulosic fibre material. 6.The method of claim 5 wherein the cellulosic fibre material is acotton-containing fibre material.